CN101678348B - Honeycomb structure - Google Patents

Honeycomb structure Download PDF

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Publication number
CN101678348B
CN101678348B CN2008800198320A CN200880019832A CN101678348B CN 101678348 B CN101678348 B CN 101678348B CN 2008800198320 A CN2008800198320 A CN 2008800198320A CN 200880019832 A CN200880019832 A CN 200880019832A CN 101678348 B CN101678348 B CN 101678348B
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Prior art keywords
zeolite
structured body
honeycomb structured
cellular unit
body according
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Expired - Fee Related
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CN2008800198320A
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Chinese (zh)
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CN101678348A (en
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大野一茂
国枝雅文
井户贵彦
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Ibiden Co Ltd
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Ibiden Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
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    • B01D53/34—Chemical or biological purification of waste gases
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    • B01J29/69—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract

The invention provides a honeycomb structure comprising a honeycomb unit containing inorganic particles and an inorganic binder and having multiple through-holes laid parallelly in the longitudinal direction thereof with a partition wall interposed therebetween and, provided on the periphery thereof, a coat layer. The coat layer has a specific heat capacity whose ratio to the specific heat capacity of the honeycomb unit is 1.0 or less.

Description

Honeycomb structured body
Technical field
The present invention relates to a kind of honeycomb structured body.
Background technology
At present, as one of system that purifies automobile exhaust gas, well-known have through using ammonia NOx to be reduced to SCR (the Selective Catalytic Reduction: system's (with reference to following) SCR) of nitrogen and water.
4NO+4NH 3+O 2→4N 2+6H 2O
6NO 2+8NH 3→7N 2+12H 2O
NO+NO 2+2NH 3→2N 2+3H 2O
In addition, in the SCR system, as the material of adsorb ammonia, well-known have a zeolite.
In addition; A kind of honeycomb structured body is disclosed in patent documentation 1; Wherein, Cellular unit comprises inorganic particle, inorfil and/or must be brilliant, and inorganic particle is more than one the particle of from the group of being made up of aluminium oxide, silica, zirconia, titanium dioxide, ceria, mullite and zeolite, selecting.
But, in containing the honeycomb structured body of inorganic particle, exist such problem, if that is: form the periphery coating in order to increase intensity, then initiation temperature (light-offtemperature) rises.
Patent documentation 1: No. 06/137149 brochure of International Publication.
Summary of the invention
The present invention proposes in view of the above problems, and its purpose is, a kind of honeycomb structured body that initiation temperature rises that when having formed the periphery coating, can suppress is provided.
The technological means that addresses the above problem is following:
Honeycomb structured body of the present invention has the cellular unit that comprises inorganic particle and inorganic binder; In said cellular unit; A plurality of through holes have been set up in parallel across partition along its length; On the periphery of said honeycomb structured body, have coating, wherein, the ratio of the specific heat capacity of said coating and the specific heat capacity of said cellular unit is below 1.0.Here, need to prove the thermal capacity of the specific heat capacity unit of the being meant apparent volume of cellular unit; The specific heat capacity of coating is meant the thermal capacity of unit volume.
In addition, more than one the particle preferably from the group of forming by aluminium oxide, silica, titanium dioxide, zirconia, ceria, mullite and their presoma and zeolite, selected of said inorganic particle.
In addition, in said cellular unit, the content of the said zeolite of unit apparent volume preferably 230g/L above, below the 270g/L.Here, need to prove that the unit apparent volume of cellular unit is meant the volume that comprises through hole.
In addition, more than one the zeolite preferably from the group of forming by zeolite beta, y-type zeolite, ferrierite, ZSM-5 type zeolite, modenite, faujasite, A type zeolite and zeolite L, selected of said zeolite.
In addition, the mol ratio of the silica of said zeolite and aluminium oxide preferably more than 30, below 50.
In addition, said zeolite is preferably used the zeolite that more than one the material from the group of being made up of Fe, Cu, Ni, Co, Zn, Mn, Ti, Ag and V, selected has carried out ion-exchange.
In addition, said zeolite comprises offspring, the average grain diameter of this offspring preferably 0.5 μ m above, below the 10 μ m.
In addition, the said inorganic binder solid constituent from be included in more than one the material of from the group of forming by alumina gel solution, dioxide/silica gel liquid solution, colloidal tio 2 solution, waterglass, sepiolite and attapulgite, selecting preferably.
In addition, said cellular unit preferably also comprises inorfil, the fiber of more than one that this inorfil is preferably selected from the group of being made up of aluminium oxide, silica, carborundum, sial, glass, potassium titanate and aluminium borate.
In addition, in said cellular unit, the aperture opening ratio in the cross section vertical with said length direction preferably more than 50%, below 65%.
In addition, in said honeycomb structured body, a plurality of said cellular units preferably bond together through tack coat.
According to the present invention, its effect is, a kind of honeycomb structured body that initiation temperature rises that when having formed the periphery coating, can suppress can be provided.
Description of drawings
Fig. 1 is the stereogram that is used to represent an example of honeycomb structured body of the present invention.
Fig. 2 A is the stereogram that is used to represent other examples of honeycomb structured body of the present invention.
Fig. 2 B is the stereogram that is used for the cellular unit of presentation graphs 2A.
Fig. 3 is the figure that is used to explain the initiation temperature assay method.
Fig. 4 be used for representing embodiment and comparative example, initiation temperature is with respect to the figure of the relation of the ratio B/A of the specific heat capacity A of the specific heat capacity B of periphery coating and cellular unit.
Symbol description:
10,20: honeycomb structured body; 11: cellular unit; 12: through hole; 13: tack coat; 14: the periphery coating; 100: Diesel engine; 200,500:DOC; 300:DPF; 400:SCR.
The specific embodiment
Below with reference to description of drawings preferred forms of the present invention.
Fig. 1 representes an example of honeycomb structured body of the present invention.In honeycomb structured body 10, comprise zeolite and inorganic binder, on partition has been set up in parallel the outer peripheral face of a cellular unit 11 of a plurality of through holes 12, formed periphery coating 14 along its length.At this moment, the ratio of the specific heat capacity of the specific heat capacity of periphery coating 14 and cellular unit 11 is below 1.0.Like this, just can suppress the rising of initiation temperature.Here, need to prove that honeycomb structured body 10 can be applied in the SCR system (for example, urea SCR system).
The ratio of the specific heat capacity of periphery coating 14 and the specific heat capacity of cellular unit 11 is preferably more than 0.7.If this ratio is less than 0.7, the thermal stress that then produces between cellular unit 11 and the periphery coating 14 possibly cause cracking.
The specific heat capacity of cellular unit 11 is 335～375J/L/K preferably.If the specific heat capacity of cellular unit 11 is less than 335J/L/K, then the temperature of cellular unit 11 possibly rise to the invalid temperature of zeolite; If greater than 375J/L/K, then initiation temperature possibly rise.
The specific heat capacity of periphery coating 14 is 270～370J/L/K preferably.If the specific heat capacity of periphery coating 14 is less than 335J/L/K, then the temperature of periphery coating 14 possibly rise to the invalid temperature of coating; If surpass 375J/L/K, then initiation temperature possibly rise.
In cellular unit 11, the zeolite content of unit apparent volume is 230～270g/L preferably.If the zeolite content of the unit apparent volume of cellular unit 11 less than 230g/L, then in order to obtain enough big NOx purifying rate, must increase the apparent volume of cellular unit 11 sometimes; If surpass 270g/L, then the intensity of cellular unit 11 maybe be not enough.
As zeolite, it is not had special qualification, can be zeolite beta, ZSM-5 type zeolite, modenite, faujasite, A type zeolite, zeolite L etc., also can use the two or more zeolite in these zeolites simultaneously.
In addition, the mol ratio of silica in the zeolite and aluminium oxide preferably 30～50.
Have again,, can carry out ion-exchange zeolite in order to improve the adsorption rate of ammonia.Cationic kind as being used for ion-exchange does not have special qualification to it, can be Fe, Cu, Ni, Co, Zn, Mn, Ti, Ag, V etc., can use the two or more material in these materials simultaneously yet.Ion exchange capacity better is 1.0～10.0 weight %, preferably 1.0～5.0 weight %.If ion exchange capacity is less than 1.0 weight %, then maybe be not obvious by the variation of the adsorption rate of the caused ammonia of ion-exchange; If greater than 10.0 weight %, structure possibly become unstable when then heating.Here, need to prove, when zeolite is carried out ion-exchange, as long as the zeolite immersion is contained in the cationic aqueous solution.
In addition, zeolite preferably comprises offspring, and the average grain diameter of the offspring of zeolite is 0.5～10 μ m preferably.If the average grain diameter of the offspring of zeolite less than 0.5 μ m, then possibly need to add a large amount of inorganic binders, with regard to being difficult to cellular unit 11 is carried out extrusion modling like this; If greater than 10 μ m, then the specific area of the zeolite in the cellular unit 11 reduces, and the purifying rate of NOx possibly descend.
Have, in order to improve intensity, cellular unit 11 can also comprise the inorganic particle except zeolite again.As the inorganic particle except zeolite; It is not had special qualification; Can be aluminium oxide, silica, titanium dioxide, zirconia, ceria, mullite and their presoma etc., also can use the two or more particle in these particles simultaneously.Wherein, especially, preferably aluminium oxide, zirconia.
The average grain diameter of the inorganic particle except zeolite is 0.5～10 μ m preferably.If this average grain diameter less than 0.5 μ m, then possibly need to add a large amount of inorganic binders, with regard to being difficult to cellular unit 11 is carried out extrusion modling like this; If greater than 10 μ m, the effect that then improves the intensity of cellular unit 11 maybe be not obvious.Here, need to prove that the inorganic particle except zeolite also can comprise offspring.
In addition, the ratio of the average grain diameter of the average grain diameter of the offspring of the inorganic particle except zeolite and the offspring of zeolite better is below 1, preferably 0.1～1.Maybe be not obvious if this ratio, then improves the effect of the intensity of cellular unit 11 greater than 1.
In cellular unit 11, the content of the inorganic particle except zeolite better is 3～30 weight %, preferably 5～20 weight %.If this content is less than 3 weight %, then the intensity of cellular unit 11 possibly descend; If surpass 30 weight %, then the zeolite content in the cellular unit 11 reduces, and the purifying rate of NOx possibly descend.
As inorganic binder; It is not had special qualification; Can be included in the solid constituent in alumina gel solution, dioxide/silica gel liquid solution, colloidal tio 2 solution, waterglass, sepiolite, the attapulgite etc., also can use the two or more solid constituent in these solid constituents simultaneously.
In cellular unit 11, the content of inorganic binder better is 5～30 weight %, preferably 10～20 weight %.If the content of inorganic binder is less than 5 weight %, then the intensity of cellular unit 11 possibly descend; If greater than 30 weight %, then possibly be difficult to cellular unit 11 is carried out moulding.
In order to improve intensity, cellular unit 11 preferably also comprises inorfil.
As inorfil; As long as can improve the intensity of cellular unit 11; It is not had special qualification, can be aluminium oxide, silica, carborundum, sial, glass, potassium titanate, aluminium borate etc., also can use the two or more material in these materials simultaneously.
The draw ratio of inorfil better is 2～1000, is more preferably 5～800, preferably 10～500.If draw ratio, then improves the effect of the intensity of cellular unit 11 less than 2 and possibly diminish.In addition, if draw ratio greater than 1000, the obstruction of mould mesh possibly take place when then waiting moulding through extrusion modling, and inorfil fractures during moulding, the effect that improves the intensity of cellular unit 11 possibly diminish.
In cellular unit 11, the content of inorfil better is 3～50 weight %, is more preferably 3～30 weight %, preferably 5～20 weight %.If the content of inorfil is less than 3 weight %, the effect that then improves the intensity of cellular unit 11 possibly diminish; If greater than 50 weight %, then the zeolite content in the cellular unit 11 reduces, and the purifying rate of NOx possibly descend.
In cellular unit 11, the aperture opening ratio in the cross section vertical preferably 50～65% with length direction.If aperture opening ratio is less than 50%, then zeolite may not be used for the purification of NOx effectively; If greater than 65%, then the intensity of honeycomb structured body 10 maybe be not enough.
In cellular unit 11, the density of the through hole 12 in the cross section vertical with length direction better is 15.5～124/cm 2, 31～93/cm preferably 2If the density of through hole 12 is less than 15.5/cm 2, then waste gas is difficult to contact with zeolite, and the NOx purifying rate of cellular unit 11 possibly descend; If greater than 124/cm 2, then the pressure loss of cellular unit 11 possibly increase.
The thickness of partition that is used to separate the through hole 12 of cellular unit 11 better is 0.10～0.50mm, preferably 0.15～0.35mm.If the thickness of partition is less than 0.10mm, then the intensity of cellular unit 11 possibly descend; If greater than 0.50mm, then waste gas is difficult to soak into the inside to partition, and zeolite may not be used for the purification of NOx effectively.
The thickness of periphery coating 14 is 0.1～2mm preferably.Maybe be not obvious if the thickness of periphery coating 14, then improves the effect of the intensity of honeycomb structured body 10 less than 0.1mm; If greater than 2mm, then the zeolite content of the unit volume of honeycomb structured body 10 reduces, and the NOx purifying rate of honeycomb structured body 10 possibly descend.
Honeycomb structured body 10 is cylindrical shapes, still, as the shape of honeycomb structured body of the present invention, it is not had special qualification, can be square column shape, cylindroid shape etc.
Have, the shape of through hole 12 is four side column shapes again, still, in the present invention, as the shape of through hole, it is not had specific qualification, can be triangular prism shape, hexagon post shapes etc.
Below an example of the manufacturing approach of honeycomb structured body 10 is described.At first; Use comprises the moulding that former slip zeolite and inorganic binder, that can also comprise inorganic particle except zeolite, inorfil etc. as required carries out extrusion modling etc.; Process living honeycomb formed article; Wherein, a plurality of through holes have been set up in parallel across partition along its length.Like this, even reduce firing temperature, the cylindrical shape cellular unit 11 that also can obtain having abundant intensity.
Here; Need to prove; In former slip, add alumina gel solution as inorganic binder, dioxide/silica gel liquid solution, colloidal tio 2 solution, waterglass, sepiolite, attapulgite etc., also can use materials two or more in these materials simultaneously.
In addition, in former slip, can suitably add organic binder bond, decentralized medium, shaping assistant etc. as required.
As organic binder bond, it is not had special qualification, can be methylcellulose, carboxymethyl cellulose, hydroxyethylcellulose, polyethylene glycol, phenolic resins, epoxy resin etc., also can use materials two or more in these materials simultaneously.Here, need to prove that the addition of organic binder bond is with respect to zeolite, the gross weight preferably 1～10% of inorganic particle, inorfil and inorganic binder except zeolite.
As decentralized medium, it is not had special qualification, can be the alcohol etc. of the organic solvent, methyl alcohol etc. of water, toluene etc., also can use the two or more material in these materials simultaneously.
As shaping assistant, it is not had special qualification, can be ethylene glycol, dextrin, aliphatic acid, fatty acid soaps and polyalcohol etc., also can use the two or more material in these materials simultaneously.
Brewable material when slurry, preferably mix, mixing, can use mixer or grater to wait and mix, also can use kneader to wait to carry out mixing.
Then, use the drying machine of microwave dryer, air drier, dielectric dryer, drying under reduced pressure machine, vacuum drier, freeze drier etc., the honeycomb formed article that obtains is carried out drying.
Afterwards, the honeycomb formed article that obtains is carried out degreasing.The degreasing condition is not had special qualification, can carry out suitable choice according to the organic kind that contains in the formed body, content, still, preferably 400 ℃, 2 hours.
Next, through the honeycomb formed article that obtains is burnt till, obtain the cellular unit 11 of cylindrical shape.Firing temperature better is 600～1200 ℃, preferably 600～1000 ℃.If firing temperature less than 600 ℃, then can not carry out sintering, the intensity of cellular unit 11 possibly descend; If greater than 1200 ℃, then sintering excessively carries out, and the reflecting point of the zeolite in the cellular unit 11 possibly reduce.
Next, on the outer peripheral face of the cellular unit 11 of cylindrical shape, apply the periphery coating and use slurry, and carry out drying, curing.Using slurry as the periphery coating, it is not had special restriction, can be the mixture etc. of mixture, inorganic binder, inorganic particle and inorfil of mixture, inorganic binder and the inorfil of inorganic binder and inorganic particle.
In addition, the periphery coating also can comprise organic binder bond with slurry.As organic binder bond, it is not had special restriction, can be polyvinyl alcohol, methylcellulose, ethyl cellulose, carboxymethyl cellulose etc., also can use the two or more material in these materials simultaneously.
The periphery coating also can comprise pore creating material with slurry.As pore creating material, it is not had special restriction, can be to be the hollow ball of the small hollow sphere of composition, spherical particulate propylene, graphite etc. with oxide series pottery, also can use the two or more material in these materials simultaneously.In addition, as hollow ball, can be alumina hollow ball, glass microvoid bulbus cordis, volcanic ash hollow ball, flying dust hollow ball (FA hollow ball), mullite hollow ball etc.
In the present invention, through using organic binder bond and pore creating material can adjust the specific heat capacity of periphery coating 14.
Next, through carrying out drying, curing with the aggregate of the cellular unit 11 of slurry, obtain the honeycomb structured body 10 of cylindrical shape to having applied the periphery coating.At this moment, if the periphery coating is then preferably carried out degreasing to it with containing organic binder bond in the slurry.The degreasing condition can be carried out suitable choice according to organic kind, content, still, and preferably 700 ℃, 20 minutes.
Fig. 2 A and Fig. 2 B represent other example of honeycomb structured body of the present invention.Here, need to prove that honeycomb structured body 20 is except being to have bondd a plurality of cellular units 11 constitute through tack coat 13; Identical with honeycomb structured body 10; Wherein, in said cellular unit, a plurality of through hole 12 is arranged side by side across partition along its length.
In cellular unit 11, the area of section in the cross section vertical with length direction is 5～50cm preferably 2If area of section is less than 5cm 2, when then the specific area of honeycomb structured body 10 reduced, the pressure loss also possibly increase; If area of section is greater than 50cm 2, the intensity of then tackling the thermal stress that produces in the cellular unit 11 maybe be not enough.
The thickness that makes the tack coat 13 that cellular unit 11 bonds together is 0.5～2mm preferably.If the thickness of tack coat 13 is less than 0.5mm, then adhesion strength maybe be not enough.In addition, if the thickness of tack coat 13 greater than 2mm, when then the specific area of honeycomb structured body 10 reduced, the pressure loss also possibly increase.
In addition, cellular unit 11 is four side column shapes, still, in the present invention, as the shape of cellular unit, it is not had special restriction, the shape that cellular unit is bonded together each other easily, for example, hexagon post shapes etc.
Below an example of the manufacturing approach of honeycomb structured body 20 is described.At first, likewise process the cellular unit 11 of four side column shapes with honeycomb structured body 10.Then, use slurry, cellular unit 11 is bonded together according to priority, and make its drying, curing, process the aggregate of cellular unit 11 through on the outer peripheral face of cellular unit 11, applying tack coat.At this moment, process after the aggregate of cellular unit 11, can its cut be become cylindrical shape, and it is ground.In addition, can be that fan-shaped or foursquare cellular unit 11 bonds together also with the cross section, process the aggregate of the cellular unit 11 of cylindrical shape.
Using slurry as tack coat, it is not had special restriction, can be the mixture etc. of mixture, inorganic binder, inorganic particle and inorfil of mixture, inorganic binder and the inorfil of inorganic binder and inorganic particle.
In addition, tack coat can also comprise organic binder bond with slurry.As organic binder bond, it is not had special qualification, can be polyvinyl alcohol, methylcellulose, ethyl cellulose, carboxymethyl cellulose etc., also can use the two or more material in these materials simultaneously.
Afterwards, apply the periphery coating at the outer peripheral face of the aggregate of the cellular unit 11 of cylindrical shape and use slurry.The periphery coating is not had special restriction with slurry, can comprise with tack coat and use the slurry identical materials, can comprise material different with it yet.In addition, the periphery coating also can have identical constituent with slurry with tack coat with slurry.
The periphery coating also can comprise pore creating material with slurry.As pore creating material, it is not had special restriction, can be to be the hollow ball of the small hollow sphere of composition, spherical acrylic resin particle, graphite etc. with oxide series pottery, also can use the two or more material in these materials simultaneously.In addition, as hollow ball, can be alumina hollow ball, glass microvoid bulbus cordis, volcanic ash hollow ball, flying dust hollow ball (FA hollow ball), mullite hollow ball etc.
Next, through carrying out drying, curing with the aggregate of the cellular unit 11 of slurry, obtain the honeycomb structured body 20 of cylindrical shape to having applied the periphery coating.At this moment, if tack coat with slurry and/or periphery coating with comprising organic binder bond in the slurry, then preferably it is carried out degreasing.The degreasing condition can be carried out suitable choice according to organic kind, content, still, and preferably 700 ℃, 20 minutes.
Here; Need to prove; Also can process after the honeycomb structured body, honeycomb structured body is immersed in to contain in the cationic aqueous solution zeolite carried out ion-exchange and make honeycomb structured body 10 and 20 through the former slip that use comprises the zeolite that does not carry out ion-exchange.
More than to comprise as the honeycomb structured body of the zeolite of inorganic particle and comprise zeolite, the honeycomb structured body of inorganic particle except zeolite is illustrated; But; Can think, also can obtain identical effect for the honeycomb structured body that only comprises as inorganic particle inorganic particle, except zeolite.
Embodiment
[embodiment 1]
At first, through will with Fe carried out 3 weight % ion-exchanges, average grain diameter is that the ratio of 2 μ m, silica/alumina is 40, specific area is 110m 2The zeolite beta 2600g of/g; Is the alumina gel solution 2600g of 20 weight % as the composition that contains inorganic binder with solid component meter; As inorfil, fiber diameter is that 6 μ m, average fiber length are the alumina fibre 780g of 100 μ m; Methylcellulose 410g as organic binder bond mixes, mixing, obtain former slip 1.Here, need to prove that Fe ion-exchange is carried out through zeolite granular being contained be immersed in the iron nitrate aqueous solution.In addition, the ion exchange capacity of zeolite is to use ICPS-8100 (Shimadzu Seisakusho Ltd.'s system) to try to achieve through the IPC luminesceence analysis.Afterwards, use single lead screw ex truding briquetting machine,, obtain the honeycomb formed article of living cylindrical shape through with former slip 1 extrusion modling.Next, after using microwave dryer and air drier to make the honeycomb formed article drying, under 400 ℃ of temperature, it is carried out 5 hours degreasing.Then, under 700 ℃ of temperature, carry out 5 hours burn till, obtaining diameter is that 143mm, length are the cellular units 11 of the cylindrical shape of 150mm.In the cellular unit that obtains 11, the aperture opening ratio in the cross section vertical with length direction is 60%, and the density of through hole is 78/cm 2, the thickness of partition is 0.25mm, the zeolite content of unit apparent volume is 250g/L.
Here, to be to use light microscope be that the area of the through hole in the quadrilateral area of 10cm is tried to achieve through the length of side of calculating cellular unit 11 to aperture opening ratio.In addition, to be to use light microscope be that the quantity of the through hole in the quadrilateral area of 10cm is tried to achieve through the length of side of measuring cellular unit 11 to the density of through hole.The mean value that the thickness of partition is to use the thickness (5 place) of the partition of light microscope through measuring cellular unit 11 to obtain is arranged again.
Secondly; Through will as inorganic particle, average grain diameter is γ type aluminium oxide 29 weight portions of 2 μ m; As inorfil, fiber diameter be 6 μ m, average fiber length be 100 μ m alumina fibre 7 weight portions, the inorganic bond agent content is alumina gel solution 34 weight portions of 20 weight % with solid component meter, as methylcellulose 5 weight portions of organic binder bond; Water 25 weight portions mix, mixing, obtain the periphery coating with slurry 1.
Have again; On the outer peripheral face of cellular unit 11, apply the periphery coating with slurry 1; So that the thickness of periphery coating 14 becomes 0.4mm, afterwards, use microwave dryer and air drier under 120 ℃ of temperature, they to be carried out drying, curing; And under 400 ℃ of temperature to its degreasing of carrying out 2 hours, process honeycomb structured body 10.Here, need to prove that the ratio of the specific heat capacity A of the specific heat capacity B of periphery coating 14 and cellular unit 11 is respectively 335J/L/K and 330J/L/K (reference table 1).
Here, specific heat capacity A and B are to use differential scanning calorimeter EVO/DSC 8230 (Rigaku corporate system) to measure.
[embodiment 2]
Through with average grain diameter being γ type aluminium oxide 24 weight portions of 2 μ m; Fiber diameter is that 6 μ m, average fiber length are alumina fibre 7 weight portions of 100 μ m; Solid constituent is alumina gel solution 34 weight portions of 20 weight %; As pore creating material, average grain diameter is acrylic resin 5 weight portions, methylcellulose 5 weight portions of 0.4 μ m, water 25 weight portions mix, mixing, obtain the periphery coating with slurry 2.
Except replacing the periphery coating with the slurry 1 with slurry 2, likewise process honeycomb structured body 10 (reference table 1) with embodiment 1 with the periphery coating.
[embodiment 3]
Through with average grain diameter being γ type aluminium oxide 19 weight portions of 2 μ m; Fiber diameter be 6 μ m, average fiber length be 100 μ m alumina fibre 7 weight portions; Solid constituent is alumina gel solution 34 weight portions of 20 weight %; Average grain diameter is acrylic resin 10 weight portions, methylcellulose 5 weight portions of 0.4 μ m, and water 25 weight portions mix, mixing, obtains the periphery coating with slurry 3.
Except replacing the periphery coating with the slurry 1 with slurry 3, likewise process honeycomb structured body 10 (reference table 1) with embodiment 1 with the periphery coating.
[embodiment 4]
At first, through will with Fe carried out 3 weight % ion-exchanges, average grain diameter is that the ratio of 2 μ m, silica/alumina is 40, specific area is 110m 2The zeolite beta 2250g of/g; Solid constituent is the alumina gel solution 2600g of 20 weight %; As the inorganic particle except zeolite, average grain diameter is the γ type aluminium oxide 550g of 2 μ m; Fiber diameter is that 6 μ m, average fiber length are the alumina fibre 780g of 100 μ m, and methylcellulose 410g mixes, mixing, obtains former slip 2.Afterwards, use single lead screw ex truding briquetting machine,, obtain the honeycomb formed article of living cylindrical shape through with former slip 2 extrusion modlings.Next, after using microwave dryer and air drier to make the honeycomb formed article drying, under 400 ℃ of temperature, it is carried out 5 hours degreasing.Then, under 700 ℃ of temperature, carry out 5 hours burn till, obtaining diameter is that 143mm, length are the cellular units 11 of the cylindrical shape of 150mm.In the cellular unit that obtains 11, the aperture opening ratio in the cross section vertical with length direction is 60%, and the density of through hole is 78/cm 2, the thickness of partition is 0.25mm, the zeolite content of unit apparent volume is 250g/L.
Secondly; Through with average grain diameter being γ type aluminium oxide 29 weight portions of 2 μ m, fiber diameter is that 6 μ m, average fiber length are alumina fibre 7 weight portions of 100 μ m, and solid constituent is dioxide/silica gel liquid solution 13 weight portions of 20 weight %; Solid constituent is alumina gel solution 21 weight portions of 20 weight %; Methylcellulose 5 weight portions, water 25 weight portions mix, mixing, obtain the periphery coating with slurry 4.
Have again; On the outer peripheral face of cellular unit 11, apply the periphery coating with slurry 4; So that the thickness of periphery coating 14 becomes 0.4mm, afterwards, use microwave dryer and air drier under 120 ℃ of temperature, they to be carried out drying, curing; And under 400 ℃ of temperature to its degreasing of carrying out 2 hours, process honeycomb structured body 10.(reference table 1).
[embodiment 5]
Except replacing the periphery coating with the slurry 4 with slurry 1, likewise process honeycomb structured body 10 (reference table 1) with embodiment 4 with the periphery coating.
[embodiment 6]
Except replacing the periphery coating with the slurry 4, likewise process honeycomb structured body 10 (reference table 1) with embodiment 4 with periphery coating slurry 2.
[embodiment 7]
Except replacing the periphery coating with the slurry 4 with slurry 3, likewise process honeycomb structured body 10 (reference table 1) with embodiment 4 with the periphery coating.
[comparative example 1]
Through with average grain diameter being γ type aluminium oxide 5 weight portions of 2 μ m; Fiber diameter is that 10 μ m, average fiber length are sial fiber 7 weight portions of 100 μ m; Solid constituent is dioxide/silica gel liquid solution 34 weight portions of 20 weight %; Methylcellulose 5 weight portions, water 25 weight portions mix, mixing, obtain the periphery coating with slurry 5.
Except replacing the periphery coating with the slurry 1 with slurry 5, likewise process honeycomb structured body 10 (reference table 1) with embodiment 1 with the periphery coating.
[comparative example 2]
Except replacing the periphery coating with the slurry 4 with slurry 5, likewise process honeycomb structured body 10 (reference table 1) with embodiment 4 with the periphery coating.
[comparative example 3]
Except replacing the periphery coating with the slurry 1 with slurry 4, likewise process honeycomb structured body 10 (reference table 1) with embodiment 1 with the periphery coating.
[table 1]
? Former slip The periphery coating is used slurry The specific heat capacity A of cellular unit [J/L/K] The specific heat capacity B of periphery coating [J/L/K] B/A Initiation temperature [℃]
Embodiment 1 1 1 335 330 0.99 158
Embodiment 2 1 2 335 305 0.91 155
Embodiment 3 1 3 335 273 0.81 145
Embodiment 4 2 4 370 365 0.99 158
Embodiment 5 2 1 370 330 0.89 153
Embodiment 6 2 2 370 305 0.82 148
Embodiment 7 2 3 370 273 0.74 140
Comparative example 1 1 5 335 500 1.49 195
Comparative example 2 2 5 370 500 1.35 185
Comparative example 3 1 4 335 365 1.09 175
[mensuration of initiation temperature]
As shown in Figure 3; Under the state that Diesel engine (1.6L direct fuel-injection engine) 100 is connected in series through blast pipe and diesel oxidation catalyst (DOC) 200, diesel particulate filter (DPF) 300, SCR 400, diesel oxidation catalyst (DOC) 500; At rotating speed is that 3000rpm, moment of torsion are to make its running under the condition of 170Nm, and sprays urea water at the blast pipe place near SCR 400 (between DPF 300 and the SCR 400).At this moment, use MEXA-1170NX (HORIBA corporate system) to flowing into nitric oxide (NO) and the nitrogen dioxide (NO of SCR 400 2) influx and nitric oxide (NO) and the nitrogen dioxide (NO that flows out from SCR 400 2) discharge measure, and to by formula:
(discharge of influx-NOx of NOx)/(influx of NOx) * 100
Represented NOx purifying rate [%] is measured (detectable limit is 0.1ppm), obtains the NOx purifying rate and be 50% o'clock temperature (initiation temperature).Here, need to prove that initiation temperature is to measure at the blast pipe place near SCR 400 (between DPF 300 and the SCR 400).In addition; As DOC 200, DPF 300, SCR 400 and DOC 500; Using is that 143.8mm, length are the honeycomb structured bodies (commodity) of 7.35mm with diameter respectively, and diameter is that 143.8mm, length are that honeycomb structured body and the diameter of honeycomb structured body (commodity), embodiment 1～7 or the comparative example 1～3 of 152.4mm is that 143.8mm, length are that the honeycomb structured body (commodity) of 50.8mm has disposed around under the state of sealing material (pad) and inserts canister (shell) interior DOC, DPF, SCR and DOC.Listed the mensuration result in the table 1.
In addition, illustrated among Fig. 4 in embodiment and the comparative example, initiation temperature is with respect to the relation of the ratio B/A of the specific heat capacity A of the specific heat capacity B of periphery coating and cellular unit.Can know that by Fig. 4 the initiation temperature of the honeycomb structured body of embodiment 1～7 is lower than the initiation temperature of the honeycomb structured body of comparative example 1～3.
Know by above, be set at below 1.0, can suppress the rising of initiation temperature through ratio with the specific heat capacity of the specific heat capacity of periphery coating 14 and cellular unit 11.

Claims (9)

1. a honeycomb structured body has coating on its periphery, and said honeycomb structured body has the cellular unit that comprises zeolite, inorganic binder and inorfil; In said cellular unit; Be set up in parallel a plurality of through holes across partition along its length, said honeycomb structured body is characterised in that
In said cellular unit, the content of the said zeolite of unit apparent volume is more than the 230g/L, below the 270g/L,
The ratio of the specific heat capacity of said coating and the specific heat capacity of said cellular unit is below 1.0.
2. honeycomb structured body according to claim 1 is characterized in that,
Said zeolite is more than one the zeolite of from the group of being made up of zeolite beta, y-type zeolite, ferrierite, ZSM-5 type zeolite, modenite, faujasite, A type zeolite and zeolite L, selecting.
3. honeycomb structured body according to claim 1 is characterized in that,
The silica of said zeolite and the mol ratio of aluminium oxide are more than 30, below 50.
4. honeycomb structured body according to claim 1 is characterized in that,
Said zeolite is a zeolite of using more than one the material selected in the group of being made up of Fe, Cu, Ni, Co, Zn, Mn, Ti, Ag and V to carry out ion-exchange.
5. honeycomb structured body according to claim 1 is characterized in that,
Said zeolite comprises offspring, and the average grain diameter of this offspring is more than the 0.5 μ m, below the 10 μ m.
6. honeycomb structured body according to claim 1 is characterized in that,
Said inorganic binder is the solid constituent in more than one the material of from be included in the group of being made up of alumina gel solution, dioxide/silica gel liquid solution, colloidal tio 2 solution, waterglass, sepiolite and attapulgite, selecting.
7. honeycomb structured body according to claim 1 is characterized in that,
Said inorfil is more than one the fiber of from the group of being made up of aluminium oxide, silica, carborundum, sial, glass, potassium titanate and aluminium borate, selecting.
8. honeycomb structured body according to claim 1 is characterized in that,
In said cellular unit, the aperture opening ratio in the cross section vertical with said length direction is more than 50%, below 65%.
9. honeycomb structured body according to claim 1 is characterized in that,
In said honeycomb structured body, a plurality of said cellular units bond together through tack coat.
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CN101678348A (en) 2010-03-24
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